12-carboxyamido-11 or 12-octadecenoic acids and esters thereof



2,847,455 Patented Aug. 12, 1958 carboxamido=IZ-octadecenoic acid and 12-carboxamido-..

2,847,455 ll-octadecenoic acid.

The dibasic 'acidsobtained from the above unsaturated H'CARBOXYAMIDO'H R IZOCTADECENOIC acid 'amides are 12-carboxy-1l-octadecenoicacid and 12- ACIDS AND ESTERS THEREOF 5 carboxy lZ-octadecenoic acid.. These acids. are prepared Thomas R. Steadman, Waban, and John O. H. Peterson, Y' gJ miXtuIe Of The above fiafboxamido LIL, Burlington, Mass, assignors to -National Research pounds W-l'thall alkali metal hydroxide. These acidshave Corporation, CambridgerMass'! a poration of Masbeen found to be particularly useful .in the production sachusetts of polyesters 'for the manufacture of plastics and paint resins. S eri3PlIE zg3 05 1957 One'specific detailed method ofproducing .the above acids is set forth in the following non-limiting examples. 5 Claims. (Cl. 260-482) Examplev I This invention relates to the production of .chemicals 15 T0 183-7 grams Percent P methyl y and in particular to the production of novel acids. 12-hy y m a fla k, 90-m1 f concentrated A principal object of the present inventionis to prepare sulfufic acld Q p F f w f fl p Over a the new chemical compounds, 12-carboxy-1l-octadcenoic l P Durlng the addltlon Teactlon acid and 12-carboxy-l2-octadecen i id} perature was not allowed to exceed 70 C. Upon com- Another object of the present invention is to illustrate P165011 0f the addition; The reaction mixture s heated the preparation of the new chemical compounds, l2-carp y @125, afld then added to 1000 grams of boxamido-ll-octadecenoic acid and-l2carboxamido-12- The YeVeTed 501id p f amounted t0 l6z-6'grams octadecenoic acid and the corresponding esters thereof. and was identlfied' as a mlxtur? of l l' other objects f the invention will in Part be obvious octadecenoic acid, l2-carboxamldo-12-octadecenolc acid and willin partlappear herelnaften and the corresponding methyl esters. The product had h invention accordingly comprises the new chemical an unsaturation value of 2.74 10- equlvalents per gram, compounds and compositions of matter possessing'the P P PF of the theoretlcal Value features and properties which are exemplifiedin the fol.-. based on the lmtial cyanohydrmlowing'detailed disclosure, and the scopeof the application of which .will be indicated in the claims. Example For a'fuller'understanding of'the nature'and objects 147,7 grams f a mixture f g; b i 0f the invention, reference Should be had following decenoic acid,. l2-carboxamido-12-octadecenoic acid and detaileddisclosure: thecorresponding methyl esters, 105 grams of sodium.

The present invention is directed to novel unsaturated hydroxide, 210 grams of water and 210 grams of diethyland the production f novel n r e ene glycol were heated at reflux until the evolution of dibasic acids therefrom. The acid-amides. are.usefuli as a onia ea ed, The reaction mixture then was acidified. chemical intermediates and as components of "resin comd th was separated 117.9 grams f a 90 percent ure. positions- These amides are Preferably P p y mixture of 12-carboXy-ll-octadecenoic acid and 12-,caracting 12-cyano-l2-hydroxys r acidofallester-"there; boxy-l2-octadecenoic acid. This material was further of with a mineral acid at temperatures which'will'effect purified byv distillation as the ethyl ester. Elemental a hydrolysis of the cyanohydrin, followed by dehydration analysis and an unsaturation value showed that the disthereof. The esters, particularlythemethyl ester of 12- tilled e ter wa essentially pure material.

cyano-lZ-hydroxystearic acid, are prefered since they are E l I generally liquids. The 12- cyano-l2 hydroxystearic acid xamp e or the esters thereof may be prepared in the manner il- 15 grams of a 90 percent pure mixture of 12-carboxylustrated in copending application Serial No. 579,713, filed ll-octadecenoic acid and l2-carboxy-l2-octadecenoic acid April 23, 1956, now U. S. Patent No. 2,830,065. in acetic acid solution was hydrogenated in the presence The amides which can be obtained from 12-cyano-12- of Adams catalyst. The recovered product, recrystallized hydroxystearic acid are l2-ca-rboxamido-12-octadecenoic from a 2 percent solution of water in acetic acid, was acid and 12-carboxamido-ll-octadecenoic acid. When an 98.8 percent pure 2-hexyltridecanedioic acid as shown by ester of 12-cyano-12-hydroxystearic acid is employed there neutral equivalent and elemental analysis. are also obtained the corresponding esters of the un- The reaction of Examples I and II can be represented saturated acid-amide. For example, there is obtained by the following equations:

OH (l: H2304 CH;(OH9)5 (CH2)10COOR FC CHa(CHz)4CH=C(CH2)luCOOR N CONH2 and CH3(OHz)5C=CH(CHl)9COOR ONH:

lNaOH OHa(CHa)4OH=C-(OH2)10COOH CH3(CH3)4CH=O(CH2)1OCOON8 00H H+ OONa and CHs(CH2)sO=CH(CH2)0COOH OH3(OH2)5C=CH(CH2)BCOON8 OOH OOONa from the methyl ester, methyl 12-carboxamido-12-octa where R and R may be a hydrogen, methyl, ethyl or like decenoate, methyl IZ-carboxamido-ll-octadecenoate, 12- group. When R corresponds to hydrogen, then R also represents a hydrogen group. When R represents an alkyl group such as methyl, then R may represent a hydrogen or an alkyl group.

When a l2-cyano-l2-hydroxystearate is employed, as the starting material, then under the present reaction conditions, only part of the carboxyalkyl (e. g., carboxymethyl) groups may be hydrolyzed. Heating the product with a dilute aqueous solution of a mineral acid, such as hydrochloric, sulfuric, nitric, phosphoric or like acids, results in complete hydrolysis of the carboxyalkyl groups without hydrolyzing the amide groups. The conversion of l2-cyano-IZ-hydroxystearic acid and esters thereof to unsaturated acid-amides takes place when aqueous solutions of mineral acids such as shown above are employed. Mineral acids with concentrations of above 50 percent and particularly above 80 percent are preferable for the hydrolysis of the cyano group. The preferred acid is sulfuric.

The temperatures employed for the conversion of the lZ-cyano-IZ-hydroxystearic acid and/or esters thereof to unsaturated acid-amides are those which favor hydrolysis of the cyanohydrin and dehydration of the resulting hydroxy compounds. The hydrolysis of the cyanohydrin is accomplished at temperatures below about 120 C. as illustrated in copending application Serial No. 628,483, filed December 17, 1956, now U. S. Patent No. 2,830,077. However, substantially complete dehydration of the resulting hydroXy compounds takes place at temperatures above about 120 C.

The dibasic acids are prepared by heating a mixture of l2-carboXamido-1l-octadecenoic acid and 12-carboxamido-l2-octadecenoic acid, or an ester thereof such as the methyl ester, with an alkali metal hydroxide. In

addition to the use of sodium hydroxide, aqueous solu-- tions of potassium hydroxide are also applicable. Aqueous solutions with an alkali metal hydroxide concentration of between about 5 percent and 50 percent by weight are quite suitable.

The reaction between the unsaturated acid-amides or unsaturated ester-amides and alkali metal hydroxide must be carried out at a temperature above 100 C., since at temperatures below 100 C. no appreciable reaction or ammonia evolution is noticed. The reaction mixture is maintained at this elevated temperature until the evolution of ammonia therefrom has ceased.

Upon completion of this latter reaction, the dibasic acids are present as alkali metal salts. The free acids can l be recovered from their salts by treatment with a suitable mineral acid such as hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid and the like. Both the unsaturated amides and the unsaturated acids absorb hydrogen in acetic acid solutions in the presence of Adams catalyst to give the following saturated derivatives:

The 2-hexyltridecanedioic acid produced is useful as plasticizers or as a component in isocyanate cross-linked resins. Simple esters of this acid can be used as synthetic lubricants.

Since certain changes may be made in the above chemical compounds and process without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

What is claimed is:

1. The chemical compounds of the general formula where R is selected from the group consisting of hydrogen and lower alkyl groups, n is a whole number of from 4 to 5, n is awhole number of from 9 to 10, and where when n is 4, n is 10 and when n is 5, n is 9, the -CONH group in each instance being attached to the 12 carbon atom.

2. The chemical compound, IZ-carboxamido-ll-octadecenoic acid.

3. The chemical compound, 12-carboXamido-l2-octadecenoic acid.

4. A new composition of matter consisting of a mixture of 12-carboXamido-1l-octadecenoic acid and 12- carboxamido-l2-octadecenoic acid.

5. A new composition of matter consisting of a mixture of 12-carboXamido-1l-octadecenoic acid, 12-carboxamido-lZ-octadecenoic acid and the methyl esters thereof.

References Cited in the file of this patent Beilstein, 4 Aufiage, 2 Band, page 800 (1920). 

1. THE CHEMICAL COMPOUNDS OF THE GENERAL FORMULA 